CN108884367A - Lamination bonding agent, laminated body and secondary cell using the bonding agent - Google Patents

Lamination bonding agent, laminated body and secondary cell using the bonding agent Download PDF

Info

Publication number
CN108884367A
CN108884367A CN201680084487.3A CN201680084487A CN108884367A CN 108884367 A CN108884367 A CN 108884367A CN 201680084487 A CN201680084487 A CN 201680084487A CN 108884367 A CN108884367 A CN 108884367A
Authority
CN
China
Prior art keywords
laminated body
polyolefin resin
bonding agent
lamination
resin
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201680084487.3A
Other languages
Chinese (zh)
Other versions
CN108884367B (en
Inventor
中村英美
松尾高年
神山达哉
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
DIC Corp
Original Assignee
Dainippon Ink and Chemicals Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=58095219&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=CN108884367(A) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Dainippon Ink and Chemicals Co Ltd filed Critical Dainippon Ink and Chemicals Co Ltd
Publication of CN108884367A publication Critical patent/CN108884367A/en
Application granted granted Critical
Publication of CN108884367B publication Critical patent/CN108884367B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/085—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/092—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising epoxy resins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
    • C09J123/10—Homopolymers or copolymers of propene
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
    • C09J123/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
    • C09J123/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/26—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers modified by chemical after-treatment
    • C09J123/28—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers modified by chemical after-treatment by reaction with halogens or compounds containing halogen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J151/06—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/102—Primary casings; Jackets or wrappings characterised by their shape or physical structure
    • H01M50/105—Pouches or flexible bags
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/116—Primary casings; Jackets or wrappings characterised by the material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/116—Primary casings; Jackets or wrappings characterised by the material
    • H01M50/117—Inorganic material
    • H01M50/119—Metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/116—Primary casings; Jackets or wrappings characterised by the material
    • H01M50/121—Organic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/116—Primary casings; Jackets or wrappings characterised by the material
    • H01M50/124—Primary casings; Jackets or wrappings characterised by the material having a layered structure
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/116—Primary casings; Jackets or wrappings characterised by the material
    • H01M50/124—Primary casings; Jackets or wrappings characterised by the material having a layered structure
    • H01M50/126—Primary casings; Jackets or wrappings characterised by the material having a layered structure comprising three or more layers
    • H01M50/129—Primary casings; Jackets or wrappings characterised by the material having a layered structure comprising three or more layers with two or more layers of only organic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/183—Sealing members
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/183—Sealing members
    • H01M50/186—Sealing members characterised by the disposition of the sealing members
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/183—Sealing members
    • H01M50/19—Sealing members characterised by the material
    • H01M50/193—Organic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/183—Sealing members
    • H01M50/19—Sealing members characterised by the material
    • H01M50/198—Sealing members characterised by the material characterised by physical properties, e.g. adhesiveness or hardness
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/10—Batteries
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/18—Fuel cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/141—Feedstock

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Electrochemistry (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Sealing Battery Cases Or Jackets (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

Problem of the present invention is that, a kind of lamination laminated body adhesive composite, its manufacturing method, laminated body and secondary cell using the bonding agent are provided, for the lamination laminated body adhesive composite, its make laminated body metal layer and plastic layer it is excellent in adhesion, electrolyte resistance is had both carrying out low temperature reservation, and its conservation rate is high, will not pass at any time and splitting occurs.This project is solved by following laminations with bonding agent, the lamination bonding agent contains polyolefin resin (A) and epoxide (B), wherein, polyolefin resin (A) is and the range that crystallization peak temperature is 28 DEG C~38 DEG C as monomer and using propylene and 1- butylene as the polymer of principal component.

Description

Lamination bonding agent, laminated body and secondary cell using the bonding agent
Technical field
It is glued the present invention relates to the bonding agent of the lamination for electrolyte used in secondary cell to be sealed, using this Connect the laminated body and secondary cell of agent.
Background technique
Positive, cathode is rendered as using lithium ion battery as the secondary cell of representative and encloses electrolyte etc. in-between It constitutes.In addition, pasting the metal foils such as aluminium foil, metal vapor deposition layer and plastics as the enclosed bag for enclosing lead Laminated body obtained by conjunction, the lead are used to take out the electricity of anode and cathode to outside.
For example, proposing a kind of enclosed bag in patent document 1, used by the innermost layer in laminated body maleic acid modified Polyolefin resin, and heat-sealing portion is constituted by same maleated polyolefin resin, so that sealing reliability be made to be improved. It is excellent with the cementability and heat sealability of metal for maleated polyolefin resin, therefore it is often used as cementability Resin.But if being used as the sealing film of battery as described above, although showing excellent glue after being just laminated at high temperature Relay, but electrolyte resistance is low, passs at any time and splitting occurs, and is not used as sealing film.
Film laminated body or battery electrode portion protective film is sealed for battery electrolyte in patent document 2 to be carried out with laminated body It records, the battery electrolyte sealing film laminated body or battery electrode portion protective film include with laminated body：Metal layer, in gold Belong to the surface surface-treated layer formed of layer and what is formed on surface-treated layer includes through carboxylic acid group or derivatives thereof modification The adhesive resin layer of polyolefin afterwards.
A kind of adhesive resin composition is described in patent document 3, it includes：(A) have selected from anhydride group, carboxyl and The polyolefin-based resins and (B) of at least one kind of functional group in carboxylic metallic salt have 2 or more epoxy groups and molecular weight is 3000 epoxidized vegetable oils below, wherein the use level of (B) ingredient is 0.01 mass parts relative to 100 mass parts of (A) ingredient ~5 mass parts.
A kind of use in electrode for secondary battery binder resin composition is described in patent document 4, which is characterized in that it contains There are acid-modified polyolefin resin (A) and polyurethane resin (B), relative to (A) 100 mass parts, (B) is 0.5 mass parts~100 matter Measure part.
Existing technical literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 09-283101 bulletin
Patent document 2：WO2007017043 bulletin
Patent document 3：Japanese Unexamined Patent Publication 08-193148 bulletin
Patent document 4：Japanese Unexamined Patent Publication 2010-277959 bulletin
Summary of the invention
Problems to be solved by the invention
Problem of the present invention is that by providing the laminating adhesive being not present in the past, to provide following lamination stackings Body adhesive composite, its manufacturing method, laminated body and secondary cell using the bonding agent, the lamination laminated body are used Adhesive composite make laminated body metal layer and plastic layer it is excellent in adhesion, have both resistance to electricity carrying out low temperature reservation Fluidity is solved, and its conservation rate is high, will not pass at any time and splitting occurs.
The method used for solving the problem
The inventors of the present invention are studied, as a result, solve the above subject with bonding agent by following laminations, it is described Lamination bonding agent contains polyolefin resin (A) and epoxide (B), wherein polyolefin resin (A) is incited somebody to action as monomer The polymer of propylene and 1- butylene as principal component, and the range that crystallization peak temperature is 28 DEG C~38 DEG C.
In addition, carrying out aging in 25~80 DEG C of range by having in the manufacturing method of bonding agent of the present invention Process, so as to provide the laminated body for being addressed project of the invention.
The effect of invention
According to the present invention, it is possible to provide following lamination laminated body adhesive composites, use the bonding agent at its manufacturing method Laminated body and secondary cell, the lamination laminated body adhesive composite makes the metal layer and plastic layer of laminated body It is excellent in adhesion, electrolyte resistance is had both carrying out low temperature reservation, conservation rate is high, will not pass at any time and layer occurs Between remove.
In addition, by having the process for carrying out aging in 25~80 DEG C of range in the manufacturing method of bonding agent, thus It is capable of providing the laminated body for being addressed project of the invention.The temperature is temperature more lower than treatment temperature up to now Degree, therefore, the cost that energy conservation when can help to through manufacture is realized reduce.
Detailed description of the invention
Fig. 1 is as the polyacrylic of standard items13The spectrogram of C-NMR.
Fig. 2 is the PB Polybutene-1 as standard items13The spectrogram of C-NMR.
Fig. 3 is the polypropylene (copolymer with ethylene) as standard items13The spectrogram of C-NMR.
Fig. 4 is the HARDREN NS-2002 used in Examples 1 to 4 as polyolefin resin (A)13C-NMR's Spectrogram.
Fig. 5 is the GMP5070E used in embodiment 5 as polyolefin resin (A)13The spectrogram of C-NMR.
Fig. 6 is the GMP3020E used in comparative example 1 as polyolefin resin (A)13The spectrogram of C-NMR.
Fig. 7 is the AUROREN 350S used in comparative example 4 as polyolefin resin (A)13The spectrogram of C-NMR.
Fig. 8 is the AUROREN 550S used in comparative example 5 as polyolefin resin (A)13The spectrogram of C-NMR.
Specific embodiment
In order to solve the above problems, the present invention is made of following projects.
1. a kind of lamination bonding agent, contains polyolefin resin (A) and epoxide (B), wherein polyolefin resin It (A) is as monomer and using propylene and 1- butylene as the polymer of principal component, crystallization peak temperature is 28 DEG C~38 DEG C Range.
2. the lamination bonding agent according to 1., wherein polyolefin resin (A) is 1~200mgKOH/g containing acid value Modified polyolefin resin, and/or hydroxyl value be 1~200mgKOH/g modified polyolefin resin.
3. according to lamination bonding agent described in 1. or 2., wherein epoxide (B) will in 1 molecule have 2 with Upper epoxy group and to have 1 or more hydroxyl and weight average molecular weight in 1 molecule be 3000 epoxides below as must It must ingredient.
4. the lamination bonding agent according to any one of 1.~3., wherein relative to said polyolefins resin (A) 100 mass parts have cooperated epoxide (B) with the ratio of 0.01~30 mass parts.
5. the lamination bonding agent according to any one of 1.~4. also contains thermoplastic elastomer (TPE), tackifiers, urges Agent, phosphate cpd, melamine resin, silane coupling agent or reactive elastomer.
6. a kind of laminated body is between metal layer and polyolefin resin layer using layer described in any one of 1.~5. Pressure with bonding agent and it is manufactured.
7. a kind of manufacturing method of laminated body, have in the manufacturing method of the laminated body described in 6. at 25~80 DEG C The process of range progress aging.
8. a kind of secondary cell will be laminated obtained from laminated body described in 6. or the manufacturing method as described in 7. Body is used as electrolyte sealing film or electrode portion protective film.
(polyolefin resin (A))
Polyolefin resin (A) of the invention is characterized in that, be as monomer and using propylene and 1- butylene as it is main at The polymer divided, and the range that crystallization peak temperature is 28 DEG C~38 DEG C.
When above-mentioned crystallization peak temperature is less than 28 DEG C, electrolyte resistance (conservation rate) is low, initial closely sealed when more than 38 DEG C Property reduce.
Polyolefin resin (A) refers to as monomer using propylene and 1- butylene as principal component：It is used as the propylene of monomer Total mole number with 1- butylene is 50% or more polymer of the molal quantity of monomer entirety.
The total mole number of particularly preferred propylene and 1- butylene is 80% or more of the molal quantity of monomer entirety.
In addition, polyolefin resin (A) of the invention is as long as monomer and using propylene and 1- butylene as principal component, so that it may With containing other monomers, such as ethylene, at this point, the preferably few polymer of molal quantity more respective than propylene and 1- butylene, into And other monomers are not contained more preferably.
Herein, the comparison as the molal quantity of propylene, 1- butylene and the ethylene of monomer for constituting polyolefin resin (A) etc. can Pass through13The peak heights of C-NMR judge.
As polyolefin resin (A) of the invention, such as copolymer of the alkene of carbon number 2~8, carbon number 2~8 can be enumerated Alkene and other monomers copolymer.
Specifically, such as high density polyethylene (HDPE) (HDPE), low density polyethylene (LDPE) (LDPE), linear low-density can be enumerated The polyethylene such as polyvinyl resin, polyisobutene, poly- (1- butylene), poly- 4- methylpentene, polyvinyl eyclohexane, gather polypropylene Styrene, poly- (p-methylstyrene), poly- (α-methylstyrene), ethylene/propylene alkene block copolymer, ethylene/propene are randomly total The alpha-olefin copolymers such as polymers, -1 copolymer of ethylene/butylene, ethylene/4 methyl 1 pentene copolymer, ethylene/hexene copolymer Object；Ethylene/vinyl acetate, ethylene/acrylic acid copolymer, ethylene/methacrylic acid methyl terpolymer, ethylene/second Vinyl acetate/methylmethacrylate copolymer, ionomer resin etc..In turn, it also can be used and these polyolefin be subjected to chlorine Chloridized polyolefin obtained by change.
In turn, polyolefin resin of the invention (A) is characterized in that, the model that crystallization peak temperature is 28 DEG C~38 DEG C It encloses.Herein, the crystallization peak temperature in the present invention is to carry out cooling resinification after heating melts, and knot when heating up again The peak temperature at crystallization peak.Herein, the peak temperature at the crystallization peak in the present invention passes through differential scanning calorimetry measuring method (DSC Method) it is measured.
In the present invention, the polyolefin resin with different crystallization peak temperatures be can be used alone, and can also combine makes With as long as its crystallization peak temperature is in the range of 28 DEG C~38 DEG C, there is no limit.
In addition, the crystallization peak heat recorded in embodiment etc. is to carry out cooling resinification after being melted by heating and rise again The value that the area at crystallization peak when warm measures.
In addition, the improved polyalkene tree that polyolefin resin (A) of the invention can be 1~200mgKOH/g containing acid value The modified polyolefin resin that rouge, and/or hydroxyl value are 1~200mgKOH/g.
Various polyolefin resins can be used in polyolefin resin used in the present invention (A) as described above, especially, more excellent It is selected as modified polyolefin resin obtained by importing various functional groups (such as carboxyl, hydroxyl etc.) into polyolefin resin.In turn, exist It among these modified polyolefin resins, is further increased from the adaptation of metal layer, the excellent aspect of electrolyte resistance is set out, more It is preferred that the modified polyolefin resin (hereinafter referred to as acid-modified polyolefin resin) and/or tool of the acid value with 1~200mgKOH/g There is the modified polyolefin resin (hereinafter referred to as hydroxyl modification polyolefin resin) of the hydroxyl value of 1~200mgKOH/g.
Acid-modified polyolefin resin refers to the polyolefin resin in molecule with carboxyl, acid anhydride, utilizes unsaturated carboxylic Acid or derivatives thereof is synthesized polyolefin modified.As the method for modifying, graft modification, copolymerization can be used.
Acid-modified polyolefin resin be by least one kind of polymerizable ethylenically unsaturated carboxylic acids or derivatives thereof graft modification or Copolymerization graft-modified polyolefin obtained by polyolefin resin before modified.As polyolefin resin before modified, can enumerate Said polyolefins resin out, wherein preferably homopolymer, propylene and the copolymer of alpha-olefin etc. of propylene.They can be independent It is used singly, or in combination of two or more kinds.
It, can as graft modification or copolymerization in the ethylenically unsaturated carboxylic acids of polyolefin resin or derivatives thereof before modified Enumerate such as acrylic acid, methacrylic acid, maleic acid, itaconic acid, citraconic acid, mesaconic acid, maleic anhydride, 4- methyl cyclohexane- 4- alkene -1,2- dicarboxylic anhydride, bicyclic [2.2.2] octyl- 5- alkene -2,3- dicarboxylic anhydride, 1,2,3,4,5,8,9,10- octahydro naphthalene -2, 3- dicarboxylic anhydride, 2- octyl- 1,3- diketone spiral shell [4.4] nonyl- 7- alkene, bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboxylic anhydride, Malaysia acyl Pimaric acid, tetrabydrophthalic anhydride, methyl-bicyclo [2.2.1] hept- 5- alkene -2,3- dicarboxylic anhydride, methyl-norborneol -5- Alkene -2,3- dicarboxylic anhydride, norborneol -5- alkene -2,3- dicarboxylic anhydride etc..It is preferable to use maleic anhydrides.They can be used alone, Or two or more is applied in combination.
In order to make the grafted monomers selected from ethylenically unsaturated carboxylic acids or derivatives thereof graft on polyolefin before modified Resin can use various methods.It can include such as following method：Polyolefin resin is melted, addition grafting is single thereto Body and the method for bringing it about graft reaction；Polyolefin resin is dissolved in solvent and solution is made, addition grafting is single thereto Body and the method for bringing it about graft reaction；The polyolefin resin for being dissolved in organic solvent and above-mentioned unsaturated carboxylic acid etc. is mixed Close, more than the softening temperature of said polyolefins resin or fusing point at a temperature of heated, carry out simultaneously in the molten state Free radical polymerization and the method for dehydrogenation reaction etc..In order to make above-mentioned grafted monomers with the progress of good efficiency in any case Graft reaction is preferably implemented in graft copolymerization in the presence of radical initiators.Graft reaction is usually in 60~350 DEG C of condition Lower progress.The use ratio of radical initiator is usually 0.001~1 relative to 100 mass parts of polyolefin resin before modified The range of mass parts.
Radical initiator can be used in bonding agent of the invention, as preferred initiator, can enumerate imidazoles system certainly By base initiator, but it is not limited to them.
Such as triphenylphosphine, 1,8- diazabicyclo (5.4.0) endecatylene -7 (DBU)-phenolate, DBU- can be enumerated Caprylate etc..
As these acid-modified polyolefin resins, such as maleic anhydride modified polypropylene, ethylene-(methyl) third can be enumerated Olefin(e) acid copolymer, ethylene-acrylate-maleic anhydride terpolymer or ethylene-methyl acrylate-maleic anhydride three Membered copolymer.Specifically, it is commercially available have Mitsubishi chemical Co., Ltd's system " MODIC ", Mitsui Chemicals, Inc's system " ADMER ", Co. Ltd. system " TOYOTAC ", Sanyo Chemical Industries Co., Ltd.'s system " YOUMEX ", Japanese polyethylene strain are spun by " UNISTOLE ", Japan Formula commercial firm system " Rexpearl EAA ", " Rexpearl ET ", DOW Chemical Company system " Primacor ", DuPont- Mitsui Polychemicals Co., Ltd. system " NUCREL ", ARKEMA system " BONDINE ".
Hydroxyl modification polyolefin resin is the polyolefin resin in molecule with hydroxyl, aftermentioned by utilizing polyolefin (methyl) acrylate of hydroxyl or the vinyl ethers of hydroxyl carry out graft modification or copolymerization to synthesize.Before modified poly- The case where olefin resin, method of modifying are with acid-modified polyolefin resin is identical.
As (methyl) acrylate of above-mentioned hydroxyl, (methyl) hydroxy-ethyl acrylate can be enumerated；(methyl) propylene Sour hydroxypropyl acrylate, (methyl) glycerol acrylate；Lactone-modified (methyl) hydroxy-ethyl acrylate, (methyl) polyalkylene glycol acrylate Ester, (methyl) acrylic acid polypropylene glycol ester etc., as the vinyl ethers of above-mentioned hydroxyl, can enumerate 2- hydroxyethylvinyl Ether, diethylene glycol monovinyl base ether, 4- hydroxybutyl vinyl ether etc..
(epoxide (B))
As epoxide (B) of the invention, can enumerate for example ethylene glycol, propylene glycol, hexylene glycol, neopentyl glycol, Trimethylolethane, trimethylolpropane, pentaerythrite, glycerol, diglycerol, D-sorbite, spiral shell glycol or hydrogenated bisphenol A etc. Polyalcohol diglycidyl ether-type epoxy resin.
In turn, diglycidyl ether-type epoxy resin, the conduct of bisphenol-A, Bisphenol F, bisphenol S, bisphenol-A D etc. can be enumerated The aromatic epoxies such as the phenolic resin varnish type epoxy resin of glycidol ether of phenol resol resins, cresol novolac resin Resin；The diglycidyl ether-type of the polyalcohols such as the ethylene oxide or propylene oxide adduct of aromatic system polyol Epoxy resin.
In turn, the bunching water that can enumerate the polyether polyol such as polyethylene glycol, polypropylene glycol or polytetramethylene glycol is sweet Oily ether type epoxy；Bis- (3,4- epoxycyclohexyl-methyl) adipate esters, 3,4- epoxycyclohexyl-methyl -3 ', 4 '-epoxide rings The annular aliphatics type poly epoxy resin such as hexyl carboxylate.
In turn, tricarballylic acid, butane tetracarboxylic acid, adipic acid, phthalic acid, terephthalic acid (TPA) or inclined benzene can be enumerated The poly glycidyl ester type epoxy resin of the polycarboxylic acids such as three acid；Butadiene, hexadiene, octadiene, 12 carbon diene, ring pungent two The bifunctional epoxy resin of the hydrocarbon systems diene such as alkene, australene or vinylcyclohexene.
In turn, the epoxy resin of the diene polymers such as polybutadiene or polyisoprene can be enumerated；Or four shrink it is sweet The double aminomethyl cyclohexanes of oil base diaminodiphenyl-methane, four glycidyl group, diglycidylaniline or four are shunk sweet The glycidyl amine type epoxy resins such as oil base m-xylene diamine；Or the ring containing various heterocycles of triazine or hydantoins etc Oxygen resin etc..
Among these, if adaptation and corrosion resistance are good using aromatic epoxy resins such as bisphenol A type epoxy resins It is good, so it is preferred that.
As concrete example, as bisphenol A type epoxy resin, can enumerate Dainippon Ink Chemicals's system " EPICLON 850,860, 1050,1055,2055 ", Mitsubishi chemical Co., Ltd's system " jER828,834,1001,1002,1004,1007 " etc..
Furthermore, it is possible to be will have 1 or more hydroxyl, simultaneously with 2 or more epoxy groups and in 1 molecule in 1 molecule And weight average molecular weight is epoxy resin of 3000 epoxides below as essential component.
It is preferred that the epoxide (B) is relative to 100 mass parts of said polyolefins resin (A) and with 0.01~30 mass parts Ratio come the situation that cooperates.
If being lower for the bonding force of substrate, it is not preferable less than 0.01 mass parts.
In addition, the cohesiveness of film is lower, and it is not preferable if being more than 30 mass parts.
(other additives)
In the present invention, as other additives, can be used known usual thermoplastic elastomer (TPE), tackifiers, catalyst, Phosphate cpd, melamine resin, silane coupling agent or reactive elastomer.The content of these additives can not damage this In the range of the function of invention bonding agent appropriate adjustment come using.
(laminated body)
Laminated body of the invention is to make the metal layers such as aluminium foil and poly- second with adhesive composite using lamination of the invention One or more plastic layers fitting in polyester such as the polyolefin pieces such as alkene, polypropylene, polyethylene terephthalate etc. obtains 's.
Also, lamination of the invention can be molten in such as ester system with arbitrary ratio dissolution/dispersion with adhesive composite In the solvent appropriate such as agent, ketone series solvent, aromatic hydrocarbon, aliphatic hydrocarbon, clicyclic hydrocarbon or dispersing agent, and use rolling method, Coating method well known to gravure coating process, stick coating method etc. is coated on metal foil and is dried, and adhesive layer is consequently formed.
The dry coating weight of lamination of the invention adhesive composite is preferably 0.5~20.0g/m2In the range of. If it is less than 0.5g/m2, then there are difficulty in terms of continuous uniform coating, on the other hand, if it exceeds 20.0g/m2, then apply Solvent release after cloth also reduces, and workability significantly reduces, and leads to the problem of residual solvent.
By being coated with lamination adhesive composite of the invention in the side of above-mentioned metal foil, then superimposed plastic layer is simultaneously It is bonded using dry lamination (dry type layered manner), thus, it is possible to obtain laminated body of the invention.The temperature of laminating roll is preferred For room temperature~120 DEG C or so, pressure is preferably 3~300kg/cm2Left and right.
In addition, laminated body of the invention preferably carries out aging after manufacturing.The preferable temperature of aging condition be 25~80 DEG C, Time is 12~240 hours, generates adhesive strength therebetween.
(secondary cell)
Laminated body of the invention can be used as the electrolyte sealing film or electrode portion protective film of one-shot battery or secondary cell, this When, make polar organic solvent and/or salt etc. and plastic layer side contacts come using.Especially, by with it is organic comprising polarity It is used in the state of the contact of the nonaqueous electrolyte of solvent and salt, to can especially function well as nonaqueous electrolyte battery, consolidate The secondary cell electrolyte sealing film or electrode for secondary battery portion protective film of body battery etc..At this point, by opposite with plastic layer Mode is folded and is sealed, and thus can be used as battery hermetic bag.The heat sealability of bonding agent used in the present invention is excellent It is different, therefore the leakage of nonaqueous electrolyte can be prevented, it can be used for a long time as battery.
As above-mentioned polar organic solvent, the polar solvent that aprotic can be enumerated, such as alkyl carbonate, ester, ketone Deng.Specifically, ethylene carbonate ester, propylene glycol carbonate, carbonic acid butanediol ester, dimethyl carbonate, carbonic acid first can be enumerated Ethyl ester, diethyl carbonate, gamma-butyrolacton, 1,2- dimethoxy-ethane, tetrahydrofuran, 2- methyltetrahydrofuran, 1,3- dioxa Penta ring, 4- methyl-1,3- dioxolane, methyl formate, formic acid 4- methyl-1,3- dioxy methyl esters, methyl acetate, methyl propionate Deng.
As salt, the alkali metal salts such as lithium salts, sodium salt, sylvite can be enumerated.As battery use, usually using LiPF6、 LiBF4, the lithium salts such as Li- acid imide.
Nonaqueous electrolyte be cyclic carbonate, linear carbonate, they the aprotic polars such as mixture it is organic molten Obtained by the above-mentioned alkali metal salt for dissolving 0.5~3mmol in agent.
Even if laminated body of the invention with above-mentioned polar solvent and/or salt, especially as their mixture It is used in the state of nonaqueous electrolyte contact, the splitting of metal layer, adhesive layer, plastic layer will not occur, it can be long-term It uses.
Battery of the invention is with the battery electrolyte sealing film or the protection of battery electrode portion being made of above-mentioned laminated body The battery of film.For battery of the invention, since splitting does not occur for above-mentioned film, and nonaqueous electrolyte can be prevented Leakage, therefore can be used steadily in the long term as battery.
For laminated body of the invention, the bonding force of metal layer and plastic layer is excellent, and for pole The endurance of property organic solvent or salt is excellent, and splitting does not occur with the contacts such as nonaqueous electrolyte.It therefore, will in this way Laminated body be used as battery electrolyte sealing film or battery electrode portion protective film battery and by such laminated body be used as two The secondary cell of primary cell electrolyte sealing film or electrode for secondary battery portion protective film can use steadily in the long term.
Embodiment
Hereinafter, specifically describing the present invention by embodiment.Stating " part " indicates mass parts.
About the structure of various polyolefin resins (A), utilize13C-NMR is analyzed, and contained list is determined according to its spectrum The structure of body.
Device name：ECX-400P (JEOL corporation)
Measure solvent：CDCl3
Measuring temperature：25℃
Integrating number：1000 times
In addition, the spectrogram of Fig. 1~3 by《The infrared absorption of principal polymeric and13C NMR spectra collection》(Japanese analytical chemistry Meeting/macromolecule analysis and research meeting of talking animatedly) it is quoted.
(embodiment 1)
It puts into 100 parts of HARDREN NS-2002,0.01 part of CUREZOL 2E4MZ, 0.5 part of DENACOL EX-321 and fills Divide and be stirred, with bar coater with 5g/m2(dry type) is coated on aluminium foil, after 80 DEG C 1 minute dry, carries out 100 with CPP film It pastes, to produce coating material.Thereafter, after its aging 5 days are made at 60 DEG C, initial bond strenght is measured.
(embodiment 2)~(embodiment 5)
Cooperate other ingredients as shown in table 1, makes bonding agent similarly to Example 1.In turn, using with laminated body 1 Identical production method makes each laminated body.
For the laminated body as obtained from each example, adhesive property, electrolyte resistance (conservation rate) are evaluated, its result is shown In table 1.
It should be noted that the condition respectively tested is as follows.
(measurement of initial bond strenght)
In the Tensilon test of (strain) A&D, sample is cut into 15mm wide, measures (180 DEG C of 180 DEG C of peel strengths N/15mm)。
(crystallization peak temperature and crystallization peak calorimetry method)
In the present invention, the measurement of crystallization peak temperature and crystallization peak heat carries out under the following conditions.
Device：Hitachi High-Tech Science/X-DSC7000
Container：Hitachi High-Tech Science/ open type aluminium vessel
Condition：Sample 5mg, control：Empty container, atmosphere：Nitrogen flow 20mL/ minutes
Measuring temperature：30 DEG C (0 minute) → -10 DEG C/min → -80 DEG C (0 minute) → 10 DEG C/min → 200 DEG C/min
(conservation rate of electrolyte resistance)
Make laminated body in electrolyte " ethylene carbonate ester：Methyl ethyl carbonate：Dimethyl carbonate=1：1：1 (wt%)+ LiPF6：1mol+ vinylene carbonate：It is impregnated 7 days in 1wt% " at 85 DEG C, as described below by the adhesive strength of dipping front and back Conservation rate carry out implementation evaluation.
○：60% or more, △：60~50%, ×：50% or less
[table 1]
HARDREN NS-2002 (Dongyang spinning company system) modified polyolefin resin nonvolatile component is 20% crystallization peak Value temperature is that 36.1 DEG C of crystallization peak heats are 20.2mj/mg
(referring to NMR spectra Fig. 4)
GMP5070E (carefree chemical company's system) modified polyolefin resin nonvolatile component is 100% crystallization peak temperature Degree is that 28.8 DEG C of crystallization peak heats are 31.0mj/mg
(referring to NMR spectra Fig. 5)
CUREZOL 2E4MZ (Shikoku Chem's system) imidazoles nonvolatile component is 100%
(SAN-APRO LTD. system) the DBU- phenolate nonvolatile component of U-CAT SA 1 is 100%
(SAN-APRO LTD. system) the DBU- caprylate nonvolatile component of U-CAT SA 102 is 100%
FTR-8120 (Mitsui Chemicals, Inc's system) tackifiers nonvolatile component is 100%
DENACOL EX-321 (Nagase ChemteX Corporation system) epoxy resin epoxy equivalent is not 140 not Volatile ingredient is 100%
(DIC Corporation system) the bisphenol A type epoxy resin epoxide equivalent of EPICLON 860 be 240 it is non-volatile at It is divided into 100%
(comparative example 1)~(comparative example 5)
As comparative example, cooperated as shown in table 2, laminated body is made in the same manner as embodiment.In turn, using the layer Stack evaluates initial bond strenght, electrolyte resistance (conservation rate).Show the result in table 2.
[table 2]
GMP3020E (carefree chemical company's system) modified polyolefin resin nonvolatile component is 100% crystallization peak temperature Degree is that 19.5 DEG C of crystallization peak heats are 16.0mj/mg
(referring to NMR spectra Fig. 6)
GMP7550E (carefree chemical company's system) modified polyolefin resin nonvolatile component is 100% crystallization peak temperature Degree is that 24.6 DEG C of crystallization peak heats are 19.1mj/mg
AUROREN 350S (Nippon Paper corporation) modified polyolefin resin nonvolatile component is 100% crystallization peak Value temperature is that 8.6 DEG C of crystallization peak heats are 3.9mj/mg
(referring to NMR spectra Fig. 7)
AUROREN 550S (Nippon Paper corporation) modified polyolefin resin nonvolatile component is 100% crystallization peak Value temperature is that 38.9 DEG C of crystallization peak heats are 37.0mj/mg
(referring to NMR spectra Fig. 8)
CUREZOL 2E4MZ (Shikoku Chem's system) imidazoles nonvolatile component is 100%
(SAN-APRO LTD. system) the DBU- phenolate nonvolatile component of U-CAT SA 1 is 100%
DENACOL EX-321 (Nagase ChemteX Corporation system) epoxy resin epoxy equivalent is not 140 not Volatile ingredient is 100%
(DIC Corporation system) the bisphenol A type epoxy resin epoxide equivalent of EPICLON 860 be 240 it is non-volatile at It is divided into 100%
Comparison by the standard items measured with NMR, the HARDREN used in embodiment as polyolefin resin (A) NS-2002, GMP5070E are as monomer and using propylene and 1- butylene as principal component, and in turn, crystallization peak temperature is 28 DEG C ~38 DEG C of range.
On the other hand, by the comparison of the standard items measured with NMR, polyolefin resin (A) is used as used in comparative example GMP3020E, GMP7550E, AUROREN 350S, AUROREN 550S as monomer and using propylene and 1- butylene as it is main at Point, but crystallization peak temperature is in outside 28 DEG C~38 DEG C of range.
It may thus be appreciated that：Even if propylene and 1- butylene are principal component as monomer by polyolefin resin (A), at crystallization peak Electrolyte resistance (conservation rate) is excellent when being worth temperature in the range of 28 DEG C~38 DEG C, is able to solve project of the invention, but Project can not be solved when outside the temperature range.
From the above results：It (is protected using the initial bond strenght of laminated body obtained from the bonding agent, electrolyte resistance Holdup) it is excellent.
Industrial availability
Lamination bonding agent of the invention makes the excellent in adhesion of metal layer and plastic layer, even if carrying out low temperature reservation Electrolyte resistance is had both, and its conservation rate is high, therefore, using laminated body obtained from the bonding agent even if progress low temperature reservation Electrolyte resistance is had both, will not pass at any time and splitting occurs, therefore, the stacking of secondary cell can be functioned well as Body.
Symbol description
a：Indicate the peak (A for being equivalent to Fig. 2) of the methyl of PB Polybutene-1
b：Indicate the peak (A for being equivalent to Fig. 1) of polyacrylic methyl
c：Indicate the peak (B for being equivalent to Fig. 1) of polyacrylic methylene
d：Indicate the peak (A for being equivalent to Fig. 3) with the methyl of the copolymer of polyethylene
e：Indicate the peak (A for being equivalent to Fig. 1) of polyacrylic methyl
f：Indicate the peak (B for being equivalent to Fig. 1) of polyacrylic methylene

Claims (8)

1. a kind of lamination bonding agent, contains polyolefin resin A and epoxide B, wherein
Polyolefin resin A is as monomer and using propylene and 1- butylene as the polymer of principal component, and crystallization peak temperature is 28 DEG C~38 DEG C of range.
2. it is according to claim 1 lamination use bonding agent, wherein polyolefin resin A contain acid value be 1mgKOH/g~ The modified polyolefin resin, and/or hydroxyl value of 200mgKOH/g is the modified polyolefin resin of 1mgKOH/g~200mgKOH/g.
3. it is according to claim 1 or 2 lamination use bonding agent, wherein epoxide B will in 1 molecule have 2 with Upper epoxy group and to have 1 or more hydroxyl and weight average molecular weight in 1 molecule be 3000 epoxides below as must It must ingredient.
4. lamination bonding agent described in any one of claim 1 to 3, wherein relative to the polyolefin resin A100 mass parts have cooperated epoxide B with 0.01 mass parts~30 mass parts ratio.
5. it is according to any one of claims 1 to 4 lamination use bonding agent, also contain thermoplastic elastomer (TPE), tackifiers, Catalyst, phosphate cpd, melamine resin, silane coupling agent or reactive elastomer.
6. a kind of laminated body is between metal layer and polyolefin resin layer using described in any one of Claims 1 to 55 It is laminated with bonding agent and manufactured laminated body.
7. a kind of manufacturing method of laminated body, have in the manufacturing method of laminated body as claimed in claim 6 25 DEG C~ The process that 80 DEG C of range carries out aging.
8. a kind of secondary cell by laminated body as claimed in claim 6 or passes through manufacturing method as claimed in claim 7 Obtained laminated body is used as electrolyte sealing film or electrode portion protective film.
CN201680084487.3A 2016-05-10 2016-05-10 Adhesive for lamination, laminate using same, and secondary battery Active CN108884367B (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/JP2016/063838 WO2017195266A1 (en) 2016-05-10 2016-05-10 Adhesive for laminates, layered body using same, and secondary battery

Publications (2)

Publication Number Publication Date
CN108884367A true CN108884367A (en) 2018-11-23
CN108884367B CN108884367B (en) 2021-03-12

Family

ID=58095219

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201680084487.3A Active CN108884367B (en) 2016-05-10 2016-05-10 Adhesive for lamination, laminate using same, and secondary battery

Country Status (7)

Country Link
US (1) US11063315B2 (en)
EP (1) EP3456793B1 (en)
JP (1) JP6083493B1 (en)
KR (1) KR102400950B1 (en)
CN (1) CN108884367B (en)
RS (1) RS64098B1 (en)
WO (1) WO2017195266A1 (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6937594B2 (en) * 2017-03-23 2021-09-22 日鉄ケミカル＆マテリアル株式会社 Adhesion imparting agent for carbon fiber reinforced resin composition
TWI785173B (en) * 2017-12-26 2022-12-01 日商迪愛生股份有限公司 Adhesives, laminates, packaging materials for batteries, and batteries
JP7420067B2 (en) * 2018-03-30 2024-01-23 東洋紡エムシー株式会社 Polyolefin adhesive composition

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015190411A1 (en) * 2014-06-11 2015-12-17 東洋紡株式会社 Polyolefin-based adhesive composition
WO2016031342A1 (en) * 2014-08-27 2016-03-03 東洋紡株式会社 Low dielectric adhesive composition
WO2016042837A1 (en) * 2014-09-17 2016-03-24 Dic株式会社 Laminate adhesive, stack using the same, and secondary battery
WO2016047289A1 (en) * 2014-09-24 2016-03-31 東亞合成株式会社 Adhesive composition and laminate with adhesive layer using same
CN107922806A (en) * 2015-08-28 2018-04-17 Dic株式会社 Lamination bonding agent, multilayer film and its secondary cell is used
CN108368402A (en) * 2016-04-27 2018-08-03 Dic株式会社 Lamination adhesive composite, laminated body and secondary cell

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3184725B2 (en) 1995-01-19 2001-07-09 昭和電工株式会社 Adhesive resin composition, laminate thereof and method for producing the same
JP3562129B2 (en) 1996-04-19 2004-09-08 住友電気工業株式会社 Encapsulation bags and lead wires for non-aqueous electrolyte batteries
DE102005037713A1 (en) 2005-08-10 2007-03-01 Daimlerchrysler Ag Drive train for a motor vehicle and method for operating a drive train
JP2010277959A (en) 2009-06-01 2010-12-09 Unitika Ltd Resin composition for binder for secondary battery electrode, binder for secondary battery electrode, electrode using binder for secondary battery electrode, and secondary battery
TWI635100B (en) * 2013-11-05 2018-09-11 三井化學股份有限公司 Modified propylene. Alpha-olefin copolymer and production method thereof, coating material containing the same, resin composition for molding, and hot-melt composition
CN105722894A (en) 2013-12-04 2016-06-29 尤尼吉可株式会社 Aqueous polyolefin resin dispersion
JP6386278B2 (en) * 2014-07-09 2018-09-05 マクセルホールディングス株式会社 Transparent thermal insulation member and method for producing the same
JP5700166B1 (en) 2014-08-01 2015-04-15 東洋インキＳｃホールディングス株式会社 Adhesive composition, laminate, storage device packaging, storage device container, and storage device
US9741467B2 (en) * 2014-08-05 2017-08-22 General Cable Technologies Corporation Fluoro copolymer coatings for overhead conductors
WO2016075975A1 (en) * 2014-11-14 2016-05-19 Dic株式会社 Adhesive for laminate, layered body, and secondary cell
JP5900680B1 (en) * 2015-03-25 2016-04-06 東洋インキＳｃホールディングス株式会社 Adhesive composition, laminate, storage device packaging, storage device container, and storage device

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015190411A1 (en) * 2014-06-11 2015-12-17 東洋紡株式会社 Polyolefin-based adhesive composition
WO2016031342A1 (en) * 2014-08-27 2016-03-03 東洋紡株式会社 Low dielectric adhesive composition
WO2016042837A1 (en) * 2014-09-17 2016-03-24 Dic株式会社 Laminate adhesive, stack using the same, and secondary battery
WO2016047289A1 (en) * 2014-09-24 2016-03-31 東亞合成株式会社 Adhesive composition and laminate with adhesive layer using same
CN107922806A (en) * 2015-08-28 2018-04-17 Dic株式会社 Lamination bonding agent, multilayer film and its secondary cell is used
CN108368402A (en) * 2016-04-27 2018-08-03 Dic株式会社 Lamination adhesive composite, laminated body and secondary cell

Also Published As

Publication number Publication date
EP3456793A4 (en) 2020-01-08
US11063315B2 (en) 2021-07-13
WO2017195266A1 (en) 2017-11-16
US20190131595A1 (en) 2019-05-02
RS64098B1 (en) 2023-04-28
EP3456793B1 (en) 2023-01-04
JP6083493B1 (en) 2017-02-22
KR20190005849A (en) 2019-01-16
EP3456793A1 (en) 2019-03-20
KR102400950B1 (en) 2022-05-23
CN108884367B (en) 2021-03-12
JPWO2017195266A1 (en) 2018-05-24

Similar Documents

Publication Publication Date Title
CN105658753B (en) Lamination adhesive, the layered product and secondary cell that have used the adhesive
JP5664836B2 (en) Laminate adhesive, laminate using the same, and secondary battery
JP6143147B1 (en) Laminate adhesive, multilayer film, and secondary battery using the same
CN108473836B (en) Adhesive composition for lamination, laminate, and secondary battery
CN108368402A (en) Lamination adhesive composite, laminated body and secondary cell
CN108884367A (en) Lamination bonding agent, laminated body and secondary cell using the bonding agent
WO2016075975A1 (en) Adhesive for laminate, layered body, and secondary cell
WO2019188284A1 (en) Polyolefin-based adhesive composition
EP3778819B1 (en) Polyolefin-based adhesive composition
TWI701862B (en) Adhesive for the laminating, the laminate using it and production method thereof, and rechargeable battery and production method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant